Specific Branched Surfactants and Consumer Products

ABSTRACT

A surfactant composition comprising one or more surfactant derivatives of isomers of acyclic detergent alcohol having 11, 16, or 21 carbon atoms and two, three, four or five methyl or ethyl branches or mixtures thereof wherein the surfactant derivatives are selected from the group consisting of cationic surfactants, zwitterionic surfactants, amine oxide surfactants, alkylpolyglycoside surfactants, soaps, fatty acids, di-long-chain alkyl cationic surfactants and mixtures

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S. patentapplication Ser. No. 12/564,428 filed Sep. 22, 2009 which claimspriority under 35 U.S.C. §119(e) to U.S. Provisional Application Ser.No. 61/098,879 filed Sep. 22, 2008.

FIELD OF THE INVENTION

The present invention relates to certain novel detergent alcohol derivedsurfactants and consumer products such as laundry products, personalcare products, dishcare products, shampoo products and hard surfacecleaning products, and the like comprising said surfactant compositions.

BACKGROUND OF THE INVENTION

Surfactants, even today, are the single most important cleaningingredient in laundry and household cleaning products. Anionicsurfactants, as a class, are the largest in terms of worldwideconsumption and typically are used at levels as high as 30 to 40% of thedetergent formulation. Other important surfactants used in consumerproducts include amine oxides, cationic surfactants, zwitterionicsurfactants, alkyl polyglycoside surfactants, soaps, and fabricsoftening cationic surfactants. These surfactants provide additionalcleaning benefits above and beyond what is provided by anionicsurfactants, as well as other benefits such as enhanced foaming,enhanced skin mildness, and fabric softening. The introduction of thepresent invention's type of polybranching into these species providesenhanced cold water cleaning performance, enhanced performance ingeneral, and process and rheology advantages. Furthermore, it is highlydesired that such materials be readily biodegradable and substantiallyderived from biomaterials to make consumer products with a bettersustainability profile.

Processes are disclosed herein to make novel surfactants useful in theformulation of consumer products such as personal care products andlaundry and cleaning products.

SUMMARY OF THE INVENTION

A surfactant composition comprising one or more surfactant derivativesof isomers of acyclic detergent alcohol having 11, 16, or 21 carbonatoms and two, three, four or five methyl or ethyl branches or mixturesthereof wherein the surfactant derivatives are selected from the groupconsisting of cationic surfactants, zwitterionic surfactants, soaps andfatty acids, amine oxide surfactants, alkylpolyglycoside surfactants,di-long-chain alkyl cationic surfactants and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to cationic surfactants, zwitterionicsurfactants, amine oxide surfactants, soaps and fatty acids,alkylpolyglycoside surfactants, di-long-chain alkyl cationic surfactantsand detergent products comprising them.

Poly-Branched Poly-Olefin Hydrophobe Structures

A key element of the process of the present invention is the feedstockpoly-branched poly-olefins which will ultimately provide the foundationto the hydrobobe of the new surfactants. To better illustrate thepossible complexity of the preferred poly-branched poly-olefinfeedstocks for the invention, structures (a) to (j) below are shown.These are only a few of hundreds of possible preferred structures thatmake up the potential feedstocks, and should not be taken as limitingthe invention.

The molecule represented by structure (d) can potentially come from adi-isoprene and is illustrative of the utility of the process to useother feedstocks than exclusively the described feedstock for thepreferred inventions.

Compound (a), (b), (c) and (e) can be derived from:

-   -   i. natural derived farnesene extracted from pre-existing plants        and organisms;    -   ii. farnesene obtained via genetically modified organisms;    -   iii. synthetically derived trimers of isoprene;    -   iv. mixtures thereof.

Other examples of illustrated poly-branched poly-olefins are shown todocument the utility of the processes of the invention to function withother olefins which may not be derived from processes i, ii, iii, or iv.These examples are less preferred.

A highly preferred olefin of the invention is (k) which can be used toconvert to the preferred alcohol of the invention.

i. Naturally Derived Farnesene Extracted from Pre-Existing Plants andOrganisms:

Examples of naturally derived farnesenes and potentially otherstructures illustrated can come from the class of natural materialscalled terpenes. Terpenes are a large and varied class of hydrocarbons,produced primarily by a wide variety of plants, particularly conifersand other pines, though also by some insects such as swallowtailbutterflies. As many of these materials isolated from plants and othernatural organisms often are present as gross mixtures, it may bedesirable to purify the components before use in the processes of theinvention. See U.S. Pat. No. 4,605,783.

The term “farnesene” refers to a set of six closely related chemicalcompounds which all are sesquiterpenes. α-Farnesene and β-farnesene areisomers, differing by the location of one double bond. α-Farnesene(structure (b) above) is 3,7,11-trimethyl-1,3,6,10-dodecatetraene andβ-farnesene (structure (a) above) is7,11-dimethyl-3-methylene-1,6,10-dodecatriene. The alpha form can existas four stereoisomers that differ about the geometry of two of its threeinternal double bonds (the stereoisomers of the third internal doublebond are identical). The beta isomer exists as two stereoisomers aboutthe geometry of its central double bond.

Two of the α-farnesene stereoisomers are reported to occur in Nature.(E,E)-α-Farnesene is the most common isomer. It is found in the coatingof apples, and other fruits. (Z,E)-α-Farnesene has been isolated fromthe oil of perilla.

β-Farnesene has one naturally occurring isomer. The E isomer is aconstituent of various essential oils. Several plants, including potatospecies, have been shown to synthesize this isomer.

ii. Farnesene Obtained Via Genetically Modified Organisms:

Several recent examples now allow for farnesene and other isoprenederivatives to be supplied via genetically modified organisms. Examplesof such sources can be found in U.S. Pat. No. 7,399,323 B2. Thisreference describes potential use of farnesene as fuel derived viagenetically engineered farnesene. Another source of geneticallyengineered farnesene and isoprenes is disclosed in U.S. Pat. No.6,872,556 B2.

iii. Synthetically Derived Trimers of Isoprene:

Synthetically derived trimers can be obtained from various sources, twoof which are shown in Japanese Patents JP 52031841 and JP 480-40705. JP480-40705 teaches a process to make compound (b) as illustrated above.The process involves oligomerization of isoprene in the presence ofdivalent Ni, phosphine derivatives, and organomagnesium compounds togive high yields i.e. 75% of compound (b). Other synthetic processes toderive trimers are available.

Mixtures of any of the above disclosed non-limiting feedstocks can beused in the processes of the invention as well as isomeric forms.

Process for Preparing a Detergent Alcohol Mixture

A first process embodiment of the present invention is a process forpreparing a detergent alcohol mixture comprising:

-   -   a. providing one or more poly-branched poly-olefins wherein the        poly-branched poly-olefins must contain one non-branched        terminal olefin and one or more additional branched olefins in        the molecule;    -   b. hydroformylating said poly-branched poly-olefins to produce a        poly-branched olefin containing aldehyde with one or more        olefins or mixture thereof, utilizing a catalyst selected from        the group IX transition metals modified or unmodified and        process conditions comprising: a process temperature ranging        from about 50° C. to about 130° C., a hydrogen to carbon        monoxide mole ratio ranging from about 0.25 to 1 to about 4 to        1, a total pressure ranging from about 300 psig to about 2000        psig;    -   c. reducing the aldehyde product of step (b) in the presence of        hydrogen and a hydrogenation catalyst, utilizing process        conditions comprising: a process temperature ranging from about        20° C. to about 130° C., a hydrogen pressure ranging from 100        psig to about 2000 psig; and    -   d. removing said poly-branched alcohol composition from said        catalyst.

This first process embodiment can be illustrated by the followingPROCESS SCHEME I which uses, as a non-limiting example, alpha farneseneas feedstock.

Selection of the olefin in process step a is previously illustratedabove. Any mixture or single material can be used from the list ofstructures or others which have the elements of being poly-branched andpoly-olefinic with one olefin not branched at a terminal position on thechain.Step 1—Hydroformylation—The one or more poly-branched poly-olefins(alpha farnesene shown here) may be reacted in the presence of hydrogen,carbon monoxide, and a Rhodium/triphenylphosphine catalyst to give thedesired poly-branched poly-olefinic aldehydes. Other Group IX metals canalso be used in this process step such as Cobalt. Cobalt and Rhodium arepreferred, but Iridium is also acceptable for the process.Carbonylhydridotris(triphenylphosphine)rhodium(I) is a metal complexwhich can be purchased from Aldrich Chemical and other sources, to beused along with triphenylphosphine. As some hydroformylation catalystsare pyrophoric it is advisable to use standard preparation methods andhandling procedures to keep oxygen levels below 40 ppm, averaging below1 ppm.

Agitation is obtained by using a PTFE coated magnetic stir bar placed inthe glass liner of the 300 ml reactor. The reactor, in turn, is placedon a magnetic stir plate that is magnetically coupled to the stir bar.Agitation rates of up to 200 rpm are possible without losing themagnetic coupling.

Unmodified Rh may also be used but may need to used at highertemperatures and pressures due to lower selectivity HRh(CO)(PPh3)2 is acatalyst which provides good selectivity particularly if used in Step 1at 25° C., 90-200 psig and with 1:1 ratio mixtures of carbon monoxideand hydrogen. Other catalysts such as HRh(CO)(PPh3)2 can also providegood selectivity if run at reaction conditions such as 80 to 100 psigand 90° C. with 1:1 ration mixtures of carbon monoxide and hydrogen andhigh ratios of excess triphenyphosine at around 800:1 relative to theRhodium. The use of rhodium with excess phosphine ligand creates anactive, selective, and stable catalyst system at 80-100 psig and 90° C.

Temperature, pressure and the ratio of carbon monoxide to hydrogen areneeded to control the reaction to provide a mono aldehyde in processstep b of the present process invention (PROCESS SCHEME 1, Step 2).Temperatures ranging from 60 to 90° C. with pressures of from 300 to 600psig and ratios of carbon monoxide to hydrogen to carbon monoxide of 2:1may be used. As noted above modified Rhodium is preferred however if onedesires to use unmodified catalyst for process step b one should useCobalt instead with it's higher reaction and ability to isomerizeolefins to give more of the desired terminal addition product. Oneshould also use higher ratios of hydrogen as well with Cobalt to avoidinternal hydroformylation producing less desired products outside thescope of this invention.

Polyaldehyde formation may be encouraged to occur by operating theprocess at a temperatures above 90° C. Higher ratios of carbon monoxideto hydrogen may also be used to maximize dialdehydes and otherpolyaldehydes.

Step 2—Reduction—In step 2, the produced poly-branched poly-olefinicaldehydes are reacted with hydrogen in the presence of a reductioncatalyst, such as nickel, to provide a substantially trimethylsubstituted saturated alcohol. Nickel on Kieselguhr is one non-limitingexample of reduction catalyst system. Rhodium on Silica, Palladium onKieselguhr are other examples of catalysts which can be used for thereduction of the poly-branched poly-olefinic aldehydes.

Process step c is carried out with a variety of catalysts ranging fromNickel on Kieselguhr Rhodium on Silica, to Palladium on Kieselguhr, andother examples of catalysts which can be used for the reduction of thepoly-branched poly-olefinic aldehydes. Reaction conditions vary from 20°C. to about 130° C., a hydrogen pressure ranging from 100 psig to about2000 psig of hydrogen and catalyst loadings can typically be in range offrom 1 to 5% on the substrate relative to the poly-branchedpoly-olefinic aldehyde. Thus, a highly efficient process is definedproviding a specific surfactant alcohol and alcohol mixtures for use inpreparation of surfactants. Reaction times will vary according tocatalyst ratio, temperature chosen and hydrogen pressure. Typicalconditions are 150° C. at 1000 psig for 16 hours in batch mode. Theprocess is not limited to batch processes. Continuous reaction can alsobe applied to the present invention. Formation of paraffin may beobserved during the sequence of processes but is readily removed bydistillation from the poly-branched poly-olefinic aldehyde after processstep c or may be also removed from the poly-branched alcohol afterperforming process step d if necessary. Thus, a highly efficient processis defined to provide a specific surfactant alcohol and alcohol mixturesfor use in preparation of surfactants. The polybranched alcoholcompositions can be converted by a number of conventional means to thesurfactant compositions such as the detergent alcohol ethoxylate, thedetergent alcohol e and detergent alcohol ethoxylated which exemplifiedin the synthesis examples.

Synthesis Example I Using Process Scheme I Synthesis of FarneseneDerived Poly-Branched Poly-Olefin Containing Aldehyde and MixturesThereof

1.6 grams of Carbonylhydridotris(triphenylphosphine)rhodium(I)[17185-29-4], 3.0 grams of Triphenylphosphine [603-35-01], and 336 gramsof a mixture of isomers of alpha-farnesene [502-61-4] are charged to a600 mL stainless steel stirred pressure vessel. The reactor is purged ofair using vacuum and nitrogen cycles then charged with a 2:1 ratiomixture of carbon monoxide and hydrogen to an initial pressure of 300psig. The reactor is heated to 85° C. with agitation with a magneticstir bar at 500 rpm and the pressure is adjusted to 600 psig using a 2:1ratio mixture of carbon monoxide and hydrogen. As carbon monoxide andhydrogen are consumed by the reaction, the pressure is maintained byusing a 1:1 ratio mixture of carbon monoxide and hydrogen. The contentsof the reactor are sampled with time and analyzed by gas chromatography(“GC”) to monitor the progress of the reaction. When the GC sampleanalysis indicates that the starting alpha-farnesene is completelyconsumed, the reaction mixture is cooled to room temperature and thecarbon monoxide: hydrogen mixture is vented. Depending on the purity ofthe alpha-farnesene, process time can run between several hours to aslong as 70 hours. Before proceeding to the next step of the reaction,residual carbon monoxide is removed by using vacuum and nitrogen cycles.The aldehyde mixture is not removed from the reactor prior to conversionto alcohol in EXAMPLE II, although the Aldehyde could be purified if sodesired or used in other reactions.

Synthesis Example II Using Process Scheme I Steps c, d Synthesis ofFarnesene Derived Poly-Branched Alcohol and Mixtures Thereof

20 grams of Nickel on Kieselguhr (60-weight % loading) and 200 mL oftetrahydrofuran are charged to a 600 mL stainless steel stirred pressurevessel. The reactor is purged of air using vacuum and nitrogen cyclesthen charged with hydrogen to an initial pressure about 600 psig. Themixture is heated to about 150° C. with stirring at 500 rpm. Hydrogen ischarged to a final pressure of about 1000 psig and maintained at thispressure for 16 hours. The contents of the reactor are then cooled toroom temperature and the pressure is reduced to about 50 psig.

The mixture obtained from Synthesis Example I is then charged to thereactor while excluding the introduction of air from the atmospherewhile continuously stirring the reactor contents. The hydroformylationcatalyst from Synthesis Example 1 may remain with the aldehyde mixtureor may be removed from the aldehyde mixture prior to use. The reactor isthen pressurized with hydrogen to an initial pressure of about 600 psigand heated to about 125° C. while agitating at about 500 rpm with amagnetic stir bar. Hydrogen pressure is then raised to 1000 psig andmaintained at this pressure. The progress of the reaction is monitoredby GC until additional product is no longer formed. The reaction timewill vary according to the reaction conditions.

Purification of the crude alcohol mixture can be achieved by standardknown procedures such as distillation or other purification methodsknown in the art.

Synthesis Example III Using Process Scheme I Synthesis of a FarneseneDerived Mixture Primarily Consisting of 4,8,12-Trimethyl-tridecan-1-ol(Alcohol 1) and 3-Ethyl-7,11-dimethyl-dodecan-1-ol (Alcohol 2) andMixtures Thereof

A 600 mL stainless steel stirred pressure vessel with magnetic stir baragitation is used as Reactor #1, using vacuum to draw in the materialswhile avoiding air. 1.80 grams ofCarbonylhydridotris(triphenylphosphine)rhodium(I) [17185-29-4] and 5.84grams of Xantphos [161265-03-8] were slurried in 77 grams of pentane andcharged to Reactor #1. The pentane is removed using vacuum and no heat,then 50 mls of toluene are added. The reactor is purged of air usingvacuum and nitrogen cycles then charged with 10 atm of a 1:1 ratiomixture of carbon monoxide and hydrogen, and heated to 60° C. for twohours and then cooled to 30° C.

The reactor is placed under vacuum then 100.86 grams oftrans-beta-Farnesene [18794-84-8] plus 50 mls of toluene are charged tothe reactor while excluding air. The reactor is purged of air usingvacuum and nitrogen cycles and then charged with about 44 atm of a 2:1ratio mixture of carbon monoxide and hydrogen. The reactor is initiallyheated to 45° C. and kept at that temperature for 19 hours. As carbonmonoxide and hydrogen are consumed by the reaction, the pressure ismaintained by using a 1:1 ratio mixture of carbon monoxide and hydrogen.

The contents of the reactor are sampled with time and analyzed by GC tomonitor the progress of the reaction. After 19 hours the reactiontemperature is increased to 85° C. while continuing the reaction for anadditional 54 hours while maintaining the pressure. Before proceeding tothe next step of the reaction, residual carbon monoxide is removed byusing heat and vacuum. At the same time, toluene is evaporated to lessthan 15% as determined by GC analysis.

A 600 mL stainless steel stirred pressure vessel is used as reactor #2.Nickel on Silica (10 grams of 64% Nickel on silica, reduced andstabilized) slurried in 50 mls of pentane is charged to Reactor #2followed by an additional 50 mls of pentane to rinse the lines. Thepentane is evaporated off using heat and vacuum. The reactor is heatedto between 270 and 275° C. while under vacuum then charged with hydrogento 150-250 psig H2 through the bottom drain port to keep that area clearof catalyst and to prevent clogging of the drain port. The reactor isallowed to stand for 15 minutes. The hydrogen is vented and the reactoris then placed under vacuum using a water aspirator. The reactor ischarged with hydrogen a second time, left for 15 minutes, then vented,and then vacuum is applied. This is repeated two more times. The reactoris then charged with hydrogen to about 250 psig (always through thebottom drain port) and the reactor is allowed to stand overnight at temp(270-275° C.) and pressure (about 250 psig H2). The reactor is thenvented, vacuum applied for 15 minutes, then recharged with hydrogen(150-250 psig) for 15 minutes. This is repeated 2 more times. Thereactor was charged with hydrogen to 250 psig then cooled to less than40° C.

The drain line of Reactor #1 is connected to Reactor #2. The contents ofReactor #1 is charged to Reactor #2 while excluding air, by pressurizingReactor #1 with hydrogen and pushing the liquid from Reactor #1 intoReactor #2 while keeping the reactor agitation at about 200 RPM.Additional hydrogen is charged to the reactor through the bottom drainport to clear the area of catalyst. The reactor is then charged withhydrogen to 150 psig (always through the bottom drain port) and thereactor was stirred at about 500 RPM. The reaction is continued untilhydrogen consumption ceases and samples drained from the reactorindicate that the reaction is complete. The reactor is heated for 24Hours at 125° C. while keeping the hydrogen pressure between 450 and 500psig H2. The product mix is drained from the reactor. The catalyst isremoved by filtration and volatile materials are removed using a rotaryevaporator. The analysis of the final mixture by gas chromatographyindicated that the mixture contains about 39%4,8,12-trimethyl-tridecan-1-ol, 34% 3-ethyl-7,11-dimethyl-dodecan-1-ol,10% total paraffin and mixed olefins, and 10% total mixed di-oxygenatedmaterials.

Synthesis Example IV Using Process Scheme I Steps a, b Synthesis ofBeta-Myrcene (C₁₁) Derived Poly-Branched Poly-Olefin Containing Aldehydeand Mixtures Thereof

1.6 grams of Carbonylhydridotris(triphenylphosphine)rhodium(I)[17185-29-4], 3.0 grams of Triphenylphosphine [603-35-0], and 336 gramsof beta-myrcene [84776-26-1], a mixture of isomers are charged to a 600mL stainless steel stirred pressure vessel. The reactor is purged of airusing vacuum and nitrogen cycles then charged with a 2:1 ratio mixtureof carbon monoxide and hydrogen to an initial pressure of 300 psig. Thereactor is heated to 85° C. with stirbar agitation at 500 rpm and thepressure adjusted to 600 psig using the 2:1 ratio mixture of carbonmonoxide and hydrogen. As carbon monoxide and hydrogen are consumed bythe reaction, the pressure is maintained by using a 1:1 ratio mixture ofcarbon monoxide and hydrogen. The contents of the reactor are sampledwith time and analyzed by GC to monitor the progress of the reaction.When the GC sample analysis indicates that the starting beta-myrcene iscompletely consumed, the reaction mixture is cooled to room temperatureand the carbon monoxide: hydrogen mixture is vented. Depending on thepurity of the beta-myrcene, the process time can vary. Before proceedingto the next step of the reaction, residual carbon monoxide is removed byusing vacuum and nitrogen cycles. The aldehyde mixture is not removedfrom the reactor prior to conversion to alcohol in EXAMPLE V, althoughthe aldehyde could be purified if so desired or used in other reactions.

Synthesis Example V Using Process Scheme I Steps c, d Synthesis ofBeta-Myrcene Derived Poly-Branched Alcohol and Mixtures Thereof

Nickel on Kieselguhr (20 grams of 60-weight % loading) plustetrahydrofuran (200 mL) are charged to a 600 mL stainless steel stirredpressure vessel. The reactor is purged of air using vacuum and nitrogencycles then charged with hydrogen to an initial pressure about 600 psig.The mixture is heated to about 150° C. with stirring at 500 rpm.Hydrogen is charged to a final pressure of about 1000 psig andmaintained at this pressure for 16 hours. The contents of the reactorare then cooled to room temperature and the pressure is reduced to about50 psig.

The aldehyde mixture obtained from SYNTHESIS EXAMPLE IV is then chargedto the reactor while excluding the introduction of air from theatmosphere while continuously stirring the reactor contents. Thehydroformylation catalyst remains with the aldehyde mixture. If sodesired the catalyst may be removed from the aldehyde mixture prior touse. The mixture is then pressurized with hydrogen at an initialpressure of about 600 psig and heated to about 125° C. while agitatingat about 500 rpm. Hydrogen pressure is then raised to 1000 psig andmaintained at this pressure while periodically sampling the reactorcontents for analysis by GC. The progress of the reaction is monitoredby GC until additional product is no longer formed. The reaction timewill vary according to the reaction conditions. Purification of thecrude alcohol mixture can be achieved by standard known procedures suchas distillation or other purification methods known in the art.

Synthesis Example VI Using Process Scheme I Synthesis of a Beta-MyrceneDerived Mixture Primarily Consisting of 4,8-dimethyl-nona-1-ol and3-Ethyl-7-methyl-octa-1-ol and Mixtures Thereof

1.80 grams of Carbonylhydridotris(triphenylphosphine)rhodium(I)[17185-29-4] and 5.84 grams of Xantphos [161265-03-8] slurried in 77grams of pentane are charged to Reactor #1, a 600 mL stainless steelstirred pressure vessel having stirbar agitation of 300-500 rpm usedthroughout, using vacuum to draw in the materials while avoiding air.The pentane is removed using vacuum and no heat. 50 mls of toluene isadded. The reactor is purged of air using vacuum and nitrogen cyclesthen charged with 10 atm of a 1:1 ratio mixture of carbon monoxide andhydrogen. It is heated to 60° C. for two hours and then cooled to 30° C.The reactor is placed under vacuum. 100.86 grams of beta-Myrcene[18794-84-8] plus 50 mls of toluene are charged to the reactor whileexcluding air. The reactor is purged of air using vacuum and nitrogencycles then charged with about 44 atm of a 2:1 ratio mixture of carbonmonoxide and hydrogen. The reactor is initially heated to 45° C. andkept at that temperature for 19 hours. As carbon monoxide and hydrogenare consumed by the reaction, the pressure is maintained by using a 1:1ratio mixture of carbon monoxide and hydrogen.

The contents of the reactor are sampled with time and analyzed by GC tomonitor the progress of the reaction. After 19 hours the reactiontemperature is increased to 85° C. while continuing the reaction for anadditional 54 hours while maintaining the pressure.

Before proceeding to the next step of the reaction, residual carbonmonoxide is removed by using heat and vacuum. At the same time, tolueneis evaporated to less than 15% by GC analysis.

Nickel on Silica (10 grams of 64% Nickel on silica, reduced andstabilized) slurried in 50 mls of pentane is charged to a 600 mLstainless steel stirred pressure vessel followed by an additional 50 mlsof pentane to rinse the lines. The pentane is evaporated off using heatand vacuum. The reactor is heated to between 270 and 275° C. while undervacuum, and then charged with hydrogen to between 150 and 250 psighydrogen through the bottom drain port to keep that area clear ofcatalyst and to prevent clogging of the drain port. The reactor isallowed to stand for 15 minutes. The hydrogen is vented and the reactoris then placed under vacuum using a water aspirator. The reactor ischarged with hydrogen, left for 15 minutes, then vented, then vacuum wasapplied. This is repeated two more times. The reactor is then chargedwith hydrogen to about 250 psig (always through the bottom drain port)and the reactor is allowed to stand overnight at temp (270-275° C.) andpressure (about 250 psig H2).

The reactor is vented and vacuum is applied for 15 minute. Then thereactor is recharged with hydrogen (150-250 psig) for 15 minutes. Thisis repeated 2 more times. The reactor is charged with hydrogen to 250psig then cooled to <40° C.

The drain line of Reactor #1 is connected to Reactor #2. The contents ofReactor #1 is charged to Reactor #2 while excluding air, by pressurizingReactor #1 with hydrogen and pushing the liquid from Reactor #1 intoReactor #2 while keeping the reactor agitation at about 200 rpm.Additional hydrogen is charged to the reactor through the bottom drainport to clear the area of catalyst. The reactor is then charged withhydrogen to 150 psig (always through the bottom drain port) and thereactor is stirred at about 500 rpm. The reaction is continued untilhydrogen consumption ceases and samples drained from the reactorindicate that the reaction is complete. The product mix is drained fromthe reactor, the catalyst is removed by filtration, and volatilematerials are removed using a rotary evaporator.

A second process embodiment represented by PROCESS SCHEME II includesthe step of selectively hydrogenating the poly-branched polyolefinbefore the hydroformylation.

Accordingly the embodiment comprises:

-   -   a. providing a poly-branched poly-olefins to a reactor;    -   b. partially and selectively hydrogenating all but one olefin of        the poly-branched poly-olefin mixture producing a poly-branched        mono-olefin mixture;    -   c. hydroformylating the poly-branched mono-olefin mixture        product of step (b) in the presence of a selective        hydroformylation catalyst and process conditions comprising: a        process temperature ranging from about 50° C. to about 130° C.,        a hydrogen to carbon monoxide mole ratio ranging from about 0.25        to 1 to about 5 to 1, a total pressure ranging from about 300        psig to about 2000 psig; producing a poly-branched aldehyde        mixture;    -   d. reducing the poly-branched aldehyde product of step (c) in        the presence of hydrogen and a metal catalyst; and    -   e. removing said poly-branched alcohol composition from said        catalyst.

In some cases, step d of this embodiment can be minimized or eveneliminated since some hydroformylation catalysts can convert the monoolefin directly to the alcohol with only minor amounts of aldehydeintermediate. With this equivalent process there may still be a need touse step d as a polishing step to convert the minor amount of aldehydeto alcohol since this aldehyde may be deleterious to reactions involvingconversion to surfactants. Examples of such catalysts are described inU.S. Pat. No. 3,420,898.

If polybranched mono-olefins from other biological or synthetic means,reaction steps a and b can be skipped and steps c and d performeddirectly.

Selective Hydrogenation—Catalysts and systems which can be used forprocess step b of PROCESS SCHEME II to give selective hydrogenation tomono olefins are described in U.S. Pat. No. 6,627,778 B2 by Xu et al. Itdescribes specific catalysts and reaction conditions to convertdiolefins to mono olefins. This process can be applied to thepoly-branched poly-olefin reaction sequence in this process embodiment.Other suitable catalysts and systems are described in U.S. Pat. Nos.4,695,560, 4,523,048, 4,520,214, 4,761,509 and Chinese Patent CN1032157. Some embodiments of the catalyst in this process may becharacterized in that it contains 1.0 to 25 wt % of nickel, 0.05 to 1.5wt % of sulfur and the support is small Al₂O₃ balls made by the oil-dropmethod, which balls have a pore volume of from 1.44 to 3.0 cm³/g, asurface area larger than 150 m²/g and have no precious metals, andessentially have no halogens, alkali earth metals and alkali metals(<0.1 wt %). Because the main active element of the catalyst used inthis process is nickel, selective hydrogenation has to be conducted at atemperature higher than 200° C. to attain a certain activity. Inaddition, in order to increase the selectivity of diolefins, tomono-olefins, it is necessary to frequently sulfurize the catalyst so asto suppress its activity.

Another approach to providing an intermediate mono olefin, if it sodesired, from step b of this process embodiment is to not control thehydrogenation, but use standard hydrogenation catalysts and allow forformation of a mixture of mono olefin and paraffin. The reaction mixturecan then be carried through the process sequence of hydroformylation cand reduction d and paraffin can be removed from the final branchedalcohol after process d by standard distillation.

For this process embodiment step c, hydroformylation, temperature,pressure and ratio of hydrogen to carbon monoxide are needed to controlthe reaction to minimize paraffin formation in this case. Preferredtemperatures range from 60 to 90° C. with pressures of from 300 to 600psig and higher ratios of carbon monoxide mixture of 2:1 or higher beingpreferred to minimize hydrogenation of the olefins to paraffins. Ratiosas low as 1:1 can also be used without substantial issue if rate is moreimportant than selectivity. As noted above modified Cobalt is preferredwith it's higher reactivity and ability to isomerize olefins to givemore of the desired terminal addition product. If one desires to useunmodified Cobalt, lower ratios of hydrogen as well should be used toavoid internal hydroformylation producing less desired products outsidethe scope of this invention.

Process step d is carried out with a variety of catalysts ranging fromNickel on Kieselguhr Rhodium on Silica, Palladium on Kieselguhr areother examples of catalysts which can be used for the reduction of thepoly-branched aldehydes. Reaction conditions vary from 20° C. to about130° C., a hydrogen pressure ranging from 100 psig to about 2000 psig ofhydrogen and catalyst loadings can typically be in range of from 1 to 5%on the substrate relative to the poly-branched poly olefinic aldehyde.Thus, a highly efficient process is defined providing a specificsurfactant alcohol and alcohol mixtures for use in preparation ofsurfactants. Reaction times will vary according to catalyst ratio,temperature chosen and hydrogen pressure. Typical conditions are 150° C.at 1000 psig for 16 hours in batch mode. The process is not limited tobatch reactions, but continuous reaction can also be applied to theinvention. Formation of paraffin may be observed during the sequence ofprocesses but is readily removed by distillation from the poly-branchedpolyolefinic alcohol after process step d or may be also removed fromthe poly-branched alcohol after performing process step e if necessary.

Synthesis Example VII Process Scheme II Synthesis of Farnesene DerivedPoly-Branched Mono-Olefin and Mixtures Thereof

Nickel on Silica catalyst (5 grams of 64% Nickel on silica, reduced andstabilized) is slurried in 50 mls of pentane and charged to a 600 mLstainless steel stirred pressure vessel followed by an additional 50 mlsof pentane to rinse the lines. The pentane is evaporated off using heatand vacuum. The reactor is heated to between 270 and 275° C. while undervacuum then charged with hydrogen to between 150 and 250 psig hydrogenthrough the bottom drain port to keep that area clear of catalyst and toprevent clogging of the drain port. The reactor is allowed to stand for15 minutes. The hydrogen is vented, and the reactor is then placed undervacuum using a water aspirator. The reactor is charged with hydrogen,left for 15 minutes, then vented, and vacuum applied. This is repeatedtwo more times. The reactor is then charged with hydrogen to about 250psig (always through the bottom drain port) and the reactor is allowedto stand overnight at temp (270-275° C.) and pressure (about 250 psigH2). The reactor is then vented, vacuum is applied to the reactor for 15minutes, and the reactor is recharged with hydrogen (150-250 psig) for15 minutes. This is repeated 2 more times. The reactor is charged withhydrogen to 250 psig then cooled to <40° C.

Trans-beta-farnesene [18794-84-8] (100 grams) is charged to a 300 mlsample cylinder followed by 50 mls of pentane to chase the lines. Thesample cylinder is connected to the 600 ml reactor with tubing andvalving. The sample cylinder is purged of atmosphere usingvacuum-hydrogen cycles. Hydrogen is introduced through the bottom of thesample cylinder and through the liquid mixture to help sparge the liquidto assist in removing low levels of air. A total of four vacuum-hydrogencycles are completed. The trans-beta-farnesene mixture is then chargedto the 600 ml reactor, while excluding air, by pressurizing the samplecylinder with hydrogen and pushing the liquid into the reactor with thereactor agitation at about 200 rpm. Additional hydrogen is charged tothe reactor through the bottom drain port to clear the area of catalyst.The reactor is then charged with hydrogen to 150 psig (always throughthe bottom drain port) and the reactor is stirred at about 500 rpm. Thereaction is continued until hydrogen consumption ceases and samplesdrained from the reactor indicate that the reaction is complete. Theproduct-pentane mix is drained from the reactor. The catalyst is removedby filtration, and the pentane is removed using a rotary evaporator.

Synthesis Example VIII Process Scheme II Using Product of Example VIISynthesis of Farnesene Derived Poly-Branched Alcohols, and MixturesThereof

1.17 mmol of Dicobalt Octacarbonyl and 4.7 mmol of Eicosyl Phobane (amixture of isomers [13887-00-8] and [13886-99-2]) are combined in 48 mlsof dried, degassed 2-propyl alcohol in a 300 mL stainless steel pressurevessel that has a glass liner and PTFE coated stir bar. 47.7 mmol of thefarnesene-derived paraffin/mono-olefin mixture obtained in SYNTHESISEXAMPLE VII, previously dried over X Ä molecular sieves and filtered, isadded to the feed tube of the reactor. The reactor lines are purged ofair using vacuum and nitrogen cycles. The 300 ml reactor is then purgedwith a 1:1 ratio mixture of carbon monoxide and hydrogen.

The reactor containing the mixture of Dicobalt Octacarbonyl, EicosylPhobane, and 2-propyl alcohol is charged to an initial pressure of about150 psig with the 1:1 ratio mixture of carbon monoxide and hydrogen. Thereactor is heated to from 60 to 65° C. with stirbar agitation at 150 to200 rpm with the pressure kept between 150 and 200 psig using a 1:1ratio mixture of carbon monoxide and hydrogen. After 1 to 2 hours thereactor is cooled to below 40° C.

The reactor is vented and the Farnesene-derived paraffin/mono-olefinmixture is charged to the reactor. The reactor is then charged with a1:2 ratio mixture of carbon monoxide and hydrogen. The reactor is thenheated to between 160 and 165° C. while keeping the pressure between 500and 700 psig using the 1:2 ratio CO:H2 gas mixture. The contents of thereactor are sampled with time and analyzed by GC to monitor the progressof the reaction. When the GC sample analysis indicates that the reactionis complete, the reaction mixture is cooled to room temperature and thecarbon monoxide-hydrogen mixture is vented.

Alcohol product may be formed directly by this catalyst and only apolishing step of hydrogenation is needed to provide stable productalcohols.

Synthesis Example IX Using Process Scheme II Step c Via PurchasedTerminal Mono Olefin of Farnesene Synthesis of4,8,12-Trimethyl-Tridecanal and Mixtures Thereof

1.22 grams of Carbonylhydridotris(triphenylphosphine)rhodium(I)[17185-29-4] and 3.11 grams of Xantphos [161265-03-8] slurried in 53grams of hexanes are charged to a 600 mL stainless steel stirredpressure vessel with stribar agitation of about 300 to 500 rpm, usingvacuum to draw in the samples while avoiding air. The reactor is purgedof air using vacuum and nitrogen cycles, then charged with 10 atm of a1:1 ratio mixture of carbon monoxide and hydrogen and heated to 60° C.for two hours, and then cooled to 30° C. The reactor is placed undervacuum. 27.4 grams of 3,7,11-Trimethyl-1-dodecene [1189-36-2] plus 85grams of toluene are charged to the reactor while excluding air. Thereactor is purged of air using vacuum and nitrogen cycles, then chargedwith 10 to 15 atm of a 2:1 ratio mixture of carbon monoxide andhydrogen. The reactor is heated to 45° C. As carbon monoxide andhydrogen are consumed by the reaction, the pressure was maintained byusing a 1:1 ratio mixture of carbon monoxide and hydrogen. The contentsof the reactor are sampled with time and analyzed by GC to monitor theprogress of the reaction. When the GC sample analysis indicates that thereaction is complete, the reaction mixture is cooled to room temperatureand the carbon monoxide:hydrogen mixture is vented.

Depending on the purity of the 3,7,11-Trimethyl-1-dodecene, process timecan run between several hours to as long as 120 hours. Before proceedingto the next step of the reaction, residual carbon monoxide is removed byusing vacuum and nitrogen cycles. The aldehyde mixture does not have tobe removed from the reactor prior to conversion to alcohol in EXAMPLEIX, although the Aldehyde could be purified if so desired or used inother reactions.

Synthesis Example X Using Process Scheme II Step d Synthesis of4,8,12-Trimethyl-tridecan-1-ol and Mixtures Thereof

Nickel on Kieselguhr (20 grams of 60-weight % loading) plustetrahydrofuran (200 mL) are charged to a 600 mL stainless steel stirredpressure vessel. The reactor is purged of air using vacuum and nitrogencycles then charged with hydrogen to an initial pressure of about 600psig. The mixture is heated to about 150° C. with stirring at about 500rpm. Hydrogen is charged to a final pressure of about 900 psig andmaintained at this pressure for 16 hours. The contents of the reactorare then cooled to room temperature and the pressure reduced to about 50psig.

The aldehyde mixture obtained from SYNTHESIS EXAMPLE VI is then chargedto the reactor while excluding the introduction of air from theatmosphere while continuously stirring the reactor contents. Thehydroformylation catalyst may remain with the aldehyde mixture. If sodesired, the catalyst may be removed from the mixture prior to use. Themixture is then pressurized with hydrogen at an initial pressure ofabout 600 psig and heated to about 125° C. while agitating at about 500rpm. Hydrogen pressure is then raised to about 900 psig and maintainedat this pressure while periodically sampling the reactor contents foranalysis by GC. The progress of the reaction is monitored by GC untiladditional product is no longer formed. The reaction time will varyaccording to the reaction conditions.

Purification of the crude alcohol mixture can be achieved by standardknown procedures such as distillation or other purification methodsknown in the art.

Another embodiment of the process of the present invention isillustrated by PROCESS SCHEME III:

This embodiment is a process according to the first embodiment where,however, the hydroformylatoin and the reduction steps are performedsimultaneously in a single step. Accordingly the process comprises:

-   -   a. providing poly-branched poly-olefins wherein the        poly-branched poly-olefins must contain one non-branched        terminal olefin and one or more additional branched olefins in        the molecule; and    -   b. hydroformylating and reducing said poly-branched poly-olefin        utilizing a catalyst selected from specific modified group IX        transition metals and process conditions comprising: a process        temperature ranging from about 90° C. to about 200° C., a        hydrogen to carbon monoxide mole ratio ranging from about 2 to 1        to about 5 to 1, a total pressure ranging from about 300 psig to        about 2000 psig; and    -   c. removing said alcohol composition from said catalyst.

In the sequences of the third process embodiment above, the selection ofthe feedstocks for a is same as for the other embodiments. In the caseof reaction step b a specialized hydroformylation catalyst is requiredand process conditions to afford maximum formation of the alcoholwithout isolation of the aldehyde. Furthermore, a key result of thisprocess is also simultaneous hydrogenation of the unreacted olefins inthe poly-branched poly-olefin feedstock. This is the most efficientprocess. However it is challenging to avoid formation of large amountsof paraffins. Catalysts of the type illustrated in U.S. Pat. No.3,420,898 are suitable catalysts for this third embodiment. Processconditions for step b require a temperature ranging from about 50° C. toabout 130° C., a hydrogen to carbon monoxide mole ratio ranging fromabout 2:1 to about 5:1, and a total pressure ranging from about 300 psigto about 2000 psig.

Catalysts preferred for this process are Cobalt based and modified withtriphenylphosphine. Addition of small amounts of Ph₂PCH₂CH₂CH₂CH₂PPh₂can aid this reaction.

Finally, step c is performed to remove the branched alcohol compositionfrom the catalyst by distillation or other means commonly used inindustry. Paraffins are formed more readily in this process and as suchdistillation is required to purify the alcohol.

Synthesis Example XI Process Scheme III Synthesis of Farnesene DerivedPoly-Branched Alcohols, and Mixtures Thereof

In a facility for operating pressurized equipment 1.17 mmol of DicobaltOctacarbonyl and 4.7 mmol of Eicosyl Phobane (a mixture of isomers[13887-00-8] and [13886-99-2]) are combined in 48 mls of dried, degassed2-propyl alcohol in a 300 mL stainless steel pressure vessel that has aglass liner and PTFE coated stir bar. 47.7 mmol of trans-beta farnesene(previously dried over X A molecular sieves and filtered) are added tothe feed tube attached to the reactor. The reactor lines are purged ofair using vacuum and nitrogen cycles. The 300 ml reactor is then purgedwith a 1:1 ratio mixture of carbon monoxide and hydrogen.

The 300 ml reactor containing the mixture of Dicobalt Octacarbonyl,Eicosyl Phobane, and 2-propyl alcohol was charged to an initial pressureof about 150 psig with the 1:1 ratio Carbon monoxide-hydrogen mixture.The reactor is heated to between about 60 and 65° C. with agitation atfrom 150 to 200 rpm and the pressure kept between 150 and 200 psig usingthe 1:1 mixture of carbon monoxide and hydrogen. After 1 to 2 hours thereactor is cooled to below 40° C.

The reactor is vented and the trans-beta-Farnesene is charged to thereactor. The feed tube is isolated from the reactor and the reactor thencharged with a 1:2 ratio mixture of carbon monoxide and hydrogen. The300 ml reactor is then heated to between 160 and 165° C. while keepingthe pressure between 500 and 700 psig using a 1:2 ratio mixture ofcarbon monoxide and hydrogen. The contents of the reactor are sampledwith time and analyzed by GC to monitor the progress of the reaction.When the GC sample analysis indicates that the reaction is complete thereaction mixture is cooled to room temperature and the carbonmonoxide:hydrogen mixture is vented. The resulting crude productcontains Alcohol 1 and Alcohol 2.

Poly-Branched Acyclic Aldehydes

Another embodiment of the invention is the formation of new acyclicaldehydes having either 16 or 21 carbon atoms and comprising at leastthree branches and three or less carbon-carbon double bonds. These novelaldehydes may have application in flavors and fragrances. Examples ofthese acyclic aldehydes include, but are not limited to3-ethyl-7,11-dimethyldodecanal; 2,3,7,11-tetramethyl-dodecanal;7,11,-dimethyl-3-vinyldodeca-6,10-dienal;8,12-dimethyltrideca-4,7,11-trienal. Other embodiments are acyclicaldehydes having one, two or three carbon-carbon double bonds where thebranches are methyl, ethyl or both. Another embodiment is where theacyclic aldehyde is saturated and the branches are methyl, ethyl orboth. The acyclic aldehydes may be blended with other materials toobtain a useful compositions.

Non-limiting examples of structures of the novel poly-branchedpoly-olefin containing aldehydes of the invention are shown below:

The four aldehydes shown below (a1-a4) are structures formed by thereaction of beta farnesene according to process embodiment one.

The below are also possible polybranched polyaldehyde structures whichmay be produced from beta farnesene by controlling the reactionconditions to maximize their production.

Polyaldehydes are converted to polyalcohols and subsequentlypoly-functionalized surfactants. It is believed that poly-branchedpolysubstituted (e.g. di-anionic) surfactants have good soil suspendingcapacity without the tendency to crystallize and have poor solubilitythat linear di-anionic surfactants tend to demonstrate.4,8,12-trimethyltridecanal (a9) is a possible aldehyde from processSCHEME II via the second process embodiment. (a10) is also anotherresulting aldehyde of the invention as well as mixtures of the two.

The below (b1-b2) are poly-branched poly-olefin containing aldehydewhich can be made from alpha farnesene. (b3) is the dialdehyde that maybe produced under certain process conditions if production of the dialdehyde is desired.

The following (C₁₁ aldehydes 1-4) are also examples of aldehydes of theprocess invention according to PROCESS SCHEME I and detailed processelements in the chain lengths of C₁₁ and C₂₁. They can form fromreaction according to process one using ocimene (1-2) and myrcene (3-4)with (aldehyde 5) coming from (Z)-3-ethyl-7-methylocta-1,3,6-triene.(C₁₁ poly-branched poly-olefin)

The following is an example of a C₂₁ poly-branched poly-olefin aldehydewhich can be derived from C₂₀ terpenes such as olefin (i).

Poly-Branched Detergent Alcohols

Another embodiment of the present invention are the poly-brancheddetergent alcohols formed by the present process which contain 11, 16 or21 carbon atoms.

Certain embodiments of the poly-branched detergent alcohols of thepresent invention include C₁₁ and C₂₁ detergent alcohols comprising two,three, four or five methyl or ethyl branches or mixtures thereof. Thesecan come via structures of diisoprenes and tetra isoprenes or otherpoly-branched poly-olefin feedstocks. They may be used in shampoos,dishwashing and/or hard surface cleaners once converted to thecorresponding surfactant compositions. Examples of these alcohols areshown below. Useful embodiments will have high levels of methylbranching, and will comprise greater than 70% two, three or four methylgroups or mixtures thereof.

Other useful embodiments include poly-branched detergent alcoholscompositions are acyclic and have a carbon atom chain length of 16. Theembodiments may have greater than 10% trimethyl branching, or greaterthan 30% trimethyl branching or even 70% or more trimethyl branching.

Embodiment of poly-branched detergent alcohols derived from naturallyderived farnesene extracted from pre-existing plants and organisms,farnesene obtained via genetically modified organisms, syntheticallyderived trimers of isoprene, mixtures thereof have been found to beuseful in cleaning compositions. Poly-branched detergent alcohols andmixtures there of may be derived from mixtures of farnesene isomers.

Although it should be understood that any isoprene based olefin of anychain length can be used to prepare a detergent alcohol mixture usingthe process of the present invention as long as the derivatives comefrom oligomers obtained from acyclic isoprene like materials by any ofthe means described above. Examples of C₁₆ poly-branched detergentalcohols are illustrated below.

The polybranched detergent alcohols of the present invention includealcohols having one or more alcohol group. The processes of the presentinvention may be optimized to control a minimized or maximized formationof a poly alcohol (di, tri and tetra alcohols) as opposed to themonoalcohol.

Synthesis Example XII Using Process Scheme I Synthesis of FarneseneDerived Poly-Branched Polyalcohols

1.17 mmol of Dicobalt Octacarbonyl and 4.7 mmol of Eicosyl Phobane (amixture of isomers [13887-00-8] and [13886-99-2]) are combined in 48 mlsof dried, degassed 2-propyl alcohol in a 300 mL stainless steel pressurevessel that has a glass liner and PTFE coated stir bar. 47.7 mmol of thetrans-beta-Farnesene (previously dried over mole sieves and filtered)are added to a feed tube attached to the reactor. The reactor lines arepurged of air using vacuum and nitrogen cycles. The reactor is thenpurged with a 1:1 ratio mixture of carbon monoxide and hydrogen. Thereactor containing the mixture of Dicobalt Octacarbonyl, EicosylPhobane, and 2-propyl alcohol is charged to an initial pressure of about150 psig with the 1:1 ratio mixture of carbon monoxide and hydrogen. Thereactor is heated to a temperature of from 60 to 65° C. with agitationat 150 to 200 rpm and the pressure is kept between 150 and 200 psigusing the 1:1 ratio mixture of carbon monoxide and hydrogen. After 1 to2 hours the reactor is cooled to below 40° C.

The reactor is vented and the contents of the feed tube(trans-beta-Farnesene) is charged to the reactor by opening the valvesseparating the two containers. The reactor is then charged with a newcarbon monoxide-hydrogen mixture consisting of a 1:2 ratio mixture ofcarbon monoxide and hydrogen. The reactor is then heated to from 160 to165° C. while keeping the pressure between 500 and 700 psig using a 1:2ratio mixture of carbon monoxide and hydrogen.

The contents of the reactor are sampled with time and analyzed by GC tomonitor the progress of the reaction. When the GC sample analysisindicates that the reaction is complete, the reaction mixture is cooledto room temperature and the carbon monoxide:hydrogen mixture is vented.The catalyst is removed and the resulting mixture contains greater than30% diols and higher polyols. The diols and higher polyols are separatedfrom the paraffins and mono alcohols by routine distillation procedure.

Poly-Branched Surfactants

Other embodiments of the present invention include surfactantcompositions derived from the poly-branched detergent alcohols oraldehydes. These can be of C₁₁, C₁₆ or C₂₁ chain lengths and bepoly-branched where the branches are methyl, ethyl or mixtures thereof.The surfactants may be formed by way of any alcohol-to-surfactant oraldehyde-to-surfactant derivatization process known in the industry.

Fatty alcohols and aldehydes may be converted into other usefulpolybranched surfactants such as cationic surfactants, zwitterionicsurfactants, amine oxide surfactants, alkylpolyglycoside surfactants,soaps, fatty acids, and di-long-chain alkyl cationic surfactants.Synthetic procedures for obtaining these materials from the parentpolybranched aldehydes or alcohols may be found in the Kirk OthmerEncyclopedia of Chemical Technology or other documents in the chemicalart.

The aforementioned cationic surfactants, zwitterionic surfactants, amineoxide surfactants, alkylpolyglycoside surfactants, soaps, fatty acids,may also be combined with nonionic (AE) and anionic (AS, AES)surfactants derived from the aforementioned polybranched alcohols. TheseAE, AS, and AES materials are described in Procter & Gamble case number11157, and involve treatment of the aforementioned polybranched alcoholswith ethylene oxide optionally followed by sulfation.

Polybranched Cationic Surfactants, Amine Oxide Surfactants, and BetaineSurfactants.

Cationic surfactants may be derived from the abovementioned detergentalcohols.Examples include but are not limited to the following materials. Theaforementioned polybranched alcohols or aldehydes may be converted intotertiary amines via direct amination via reaction with secondary aminessuch as monoethanol amine (to provide the polybranched methyl,hydroxyethyl tertiary amine) or dimethyl amine (to provide thepolybranched dimethyl tertiary amine). These processes are via directamination in the presence of the amine at 230° C. at atmosphericpressure (0.1-0.5 MPa) using copper chromite catalysts (from thepolybranched alcohol) or noble metal, copper chelate, or coppercarboxylate catalysts (from the polybranched aldehydes). The resultingpolybranched tertiary amines are then converted to the hydroxyalkyl quator trimethyl quats via reaction with methyl chloride or dimethylsulfate.

Alternatively, to prepare the following amine oxides, the aforementionedpolybranched tertiary amine is oxidized with hydrogen peroxide in waterwith bicarbonate buffer.

Alternatively, to prepare the following zwitterionic betainesurfactants, the aforementioned polybranched tertiary amine is reactedwith 1,3-propane sultone, typically in acetone.

The amine oxides are highly desirable for their grease cleaning andfoaming abilities, and these properties are enhanced by the branching ofthe present invention:

Polybranched zwitterionic surfactants—The betaine classes of surfactantsare also useful in enhancing the performance of the primary, mainframesurfactant, and having them derived from natural farnesene or isoprenoidsources provides additional sustability benefits as well as enhancedcold water performance, and formulability:

Polybranched Fatty Acids and Soaps.

Soaps and fatty acids are sometimes used in laundry detergents asadjunct surfactants, or as additives to provide mildness and othersensorial benefits. When soaps and fatty acids contain theaforementioned polybranched moieties, they gain important advantages insolubility. The following polybranched fatty acids and soaps areprepared via oxidation of the aforementioned polybranched aldehydes oralcohols via any of a number of oxidizing agents such as potassiumpermangenate, Jones reagent, or other techniques known in the art. (X═Naor other counterion, or hydrogen.)

Polybranched Alkylpolyglycoside Surfactants—

The alkylpolyglycosides are particularly desirable for their mildnessand foaming ability. When incorporated with the farnesene-derived alkylmoieties, they gain additional advantages in performance such asimproved cold water solubility. The following alkyl polyglycosides(n=0-4) are prepared from the aforementioned polybranched alcohols viaacid-catalyzed reaction with monosaccharides according to U.S. Pat. No.4,950,743.

Polybranched Dialkyl Cationic Surfactants (Fabric Softener Actives)—

Fabric softener actives may be derived from the abovementionedpolybranched alcohols, and have advantages in phase stability andcompaction, as well as excellent fabric softening. Thedi(polybranched-alkyl)-dimethyl quats may be prepared via directamination of the aforementioned polybranched alcohols or aldehydes viareaction at high temperature with methyl amine [using copper chromitecatalysts (from the polybranched alcohol) or noble metal, copperchelate, or copper carboxylate catalysts (from the polybranchedaldehydes)], followed by quaternization with methyl chloride or dimethylsulfate. The di(polybranched) diester quats are prepared by oxidation ofthe aforementioned polybranched alcohols or aldehydes with any of anumber of oxidizing agents such as potassium permangenate, Jonesreagent, or other techniques known in the art, followed bydiesterification of N-methyldiethanolamine with the resultingpolybranched carboxylic acids, followed by quaternization with methylchloride or dimenthyl sulfate.

The esterquat class of fabric softener actives also gains process andsoftening advantages by incorporating the branched hydrophobes accordingto the present invention:

Surfactant Compositions and Products Using the Poly-Branched DetergentAlcohol Derivatives and Surfactant Compositions

The poly-branched surfactant composition comprising one or morederivatives of the detergent alcohol selected from the cationic, amineoxide, zwitterionic, or the alkylpolyglycosides or mixtures thereof areoutstandingly suitable as soil detachment and suspending promotingadditives for laundry and other cleaning compositions. The dialkyl ordiester quats are particularly well suited for fabric softenercompositions.

The poly-branched surfactant compositions according to the presentinvention can be added to the laundry detergents, cleaning compositions,and fabric softener compositions in amounts of generally from 0.05 to70% by weight, preferably from 0.1 to 40% by weight and more preferablyfrom 0.25 to 10% by weight, based on the particular overall composition.

In addition, the laundry detergents and cleaning compositions generallycomprise surfactants and, if appropriate, other polymers as washingsubstances, builders and further customary ingredients, for examplecobuilders, cleaning polymers (modified and unmodified polycarboxylates,ethoxylated amines and derivatives thereof), complexing agents,bleaches, standardizers, graying inhibitors, dye transfer inhibitors,enzymes and perfumes.

The novel surfactant compositions of the present invention may beutilized in laundry detergents or cleaning compositions comprising asurfactant system comprising C₁₀-C₁₅ alkyl benzene sulfonates (LAS) andone or more co-surfactants selected from nonionic, cationic, anionic ormixtures thereof. The selection of co-surfactant may be dependent uponthe desired benefit. In one embodiment, the co-surfactant is selected asa nonionic surfactant, preferably C₁₂-C₁₈ alkyl ethoxylates. In anotherembodiment, the co-surfactant is selected as an anionic surfactant,preferably C₁₀-C₁₈ alkyl alkoxy es (AE_(x)S) wherein x is from 1-30. Inanother embodiment the co-surfactant is selected as a cationicsurfactant, preferably dimethyl hydroxyethyl lauryl ammonium chloride.If the surfactant system comprises C₁₀-C₁₅ alkyl benzene sulfonates(LAS), the LAS is used at levels ranging from about 9% to about 25%, orfrom about 13% to about 25%, or from about 15% to about 23% by weight ofthe composition.

The surfactant system may comprise from 0% to about 7%, or from about0.1% to about 5%, or from about 1% to about 4% by weight of thecomposition of a co-surfactant selected from a nonionic co-surfactant,cationic co-surfactant, anionic co-surfactant and any mixture thereof.

Non-limiting examples of nonionic co-surfactants include: C₁₂-C₁₈ alkylethoxylates, such as, NEODOL® nonionic surfactants from Shell; C₆-C₁₂alkyl phenol alkoxylates wherein the alkoxylate units are a mixture ofethyleneoxy and propyleneoxy units; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkylphenol condensates with ethylene oxide/propylene oxide block alkylpolyamine ethoxylates such as PLURONIC® from BASF; C₁₄-C₂₂ mid-chainbranched alcohols, BA, as discussed in U.S. Pat. No. 6,150,322; C₁₄-C₂₂mid-chain branched alkyl alkoxylates, BAE_(x), wherein x is from 1-30,as discussed in U.S. Pat. No. 6,153,577, U.S. Pat. No. 6,020,303 andU.S. Pat. No. 6,093,856; alkylpolysaccharides as discussed in U.S. Pat.No. 4,565,647 Llenado, issued Jan. 26, 1986; specificallyalkylpolyglycosides as discussed in U.S. Pat. No. 4,483,780 and U.S.Pat. No. 4,483,779; polyhydroxy detergent acid amides as discussed inU.S. Pat. No. 5,332,528; and ether capped poly(oxyalkylated) alcoholsurfactants as discussed in U.S. Pat. No. 6,482,994 and WO 01/42408.

Non-limiting examples of semi-polar nonionic co-surfactants include:water-soluble amine oxides containing one alkyl moiety of from about 10to about 18 carbon atoms and 2 moieties selected from the groupconsisting of alkyl moieties and hydroxyalkyl moieties containing fromabout 1 to about 3 carbon atoms; water-soluble phosphine oxidescontaining one alkyl moiety of from about 10 to about 18 carbon atomsand 2 moieties selected from the group consisting of alkyl moieties andhydroxyalkyl moieties containing from about 1 to about 3 carbon atoms;and water-soluble sulfoxides containing one alkyl moiety of from about10 to about 18 carbon atoms and a moiety selected from the groupconsisting of alkyl moieties and hydroxyalkyl moieties of from about 1to about 3 carbon atoms. See WO 01/32816, U.S. Pat. No. 4,681,704, andU.S. Pat. No. 4,133,779.

Non-limiting examples of cationic co-surfactants include: the quaternaryammonium surfactants, which can have up to 26 carbon atoms include:alkoxylate quaternary ammonium (AQA) surfactants as discussed in U.S.Pat. No. 6,136,769; dimethyl hydroxyethyl quaternary ammonium asdiscussed in U.S. Pat. No. 6,004,922; dimethyl hydroxyethyl laurylammonium chloride; polyamine cationic surfactants as discussed in WO98/35002, WO 98/35003, WO 98/35004, WO 98/35005, and WO 98/35006;cationic ester surfactants as discussed in U.S. Pat. Nos. 4,228,042,4,239,660 4,260,529 and U.S. Pat. No. 6,022,844; and amino surfactantsas discussed in U.S. Pat. No. 6,221,825 and WO 00/47708, specificallyamido propyldimethyl amine (APA).

Nonlimiting examples of anionic co-surfactants useful herein include:C₁₀-C₂₀ primary, branched chain and random alkyl es (AS); C₁₀-C₁₈secondary (2,3) alkyl es; C₁₀-C₁₈ alkyl alkoxy es (AE_(x)S) wherein x isfrom 1-30; C₁₀-C₁₈ alkyl alkoxy carboxylates comprising 1-5 ethoxyunits; mid-chain branched alkyl es as discussed in U.S. Pat. No.6,020,303 and U.S. Pat. No. 6,060,443; mid-chain branched alkyl alkoxyes as discussed in U.S. Pat. No. 6,008,181 and U.S. Pat. No. 6,020,303;modified alkylbenzene sulfonate (MLAS) as discussed in WO 99/05243, WO99/05242 and WO 99/05244; methyl ester sulfonate (MES); and alpha-olefinsulfonate (AOS).

The present invention may also relates to compositions comprising theinventive surfactant composition of the sixth embodiment and a seventhembodiment, a surfactant composition comprising C₈-C₁₈ linear alkylsulfonate surfactant and a co-surfactant. The compositions can be in anyform, namely, in the form of a liquid; a solid such as a powder,granules, agglomerate, paste, tablet, pouches, bar, gel; an emulsion;types delivered in dual-compartment containers; a spray or foamdetergent; premoistened wipes (i.e., the cleaning composition incombination with a nonwoven material such as that discussed in U.S. Pat.No. 6,121,165, Mackey, et al.); dry wipes (i.e., the cleaningcomposition in combination with a nonwoven materials, such as thatdiscussed in U.S. Pat. No. 5,980,931, Fowler, et al.) activated withwater by a consumer; and other homogeneous or multiphase consumercleaning product forms.

In embodiment seven, the cleaning composition of the present inventionis a liquid or solid laundry detergent composition. In another seventhembodiment, the cleaning composition of the present invention is a hardsurface cleaning composition, preferably wherein the hard surfacecleaning composition impregnates a nonwoven substrate. As used herein“impregnate” means that the hard surface cleaning composition is placedin contact with a nonwoven substrate such that at least a portion of thenonwoven substrate is penetrated by the hard surface cleaningcomposition, preferably the hard surface cleaning composition saturatesthe nonwoven substrate. The cleaning composition may also be utilized incar care compositions, for cleaning various surfaces such as hard wood,tile, ceramic, plastic, leather, metal, glass. This cleaning compositioncould be also designed to be used in a personal care and pet carecompositions such as shampoo composition, body wash, liquid or solidsoap and other cleaning composition in which surfactant comes intocontact with free hardness and in all compositions that require hardnesstolerant surfactant system, such as oil drilling compositions.

In another seventh embodiment the cleaning composition is a dishcleaning composition, such as liquid hand dishwashing compositions,solid automatic dishwashing compositions, liquid automatic dishwashingcompositions, and tab/unit does forms of automatic dishwashingcompositions.

Quite typically, cleaning compositions herein such as laundrydetergents, laundry detergent additives, hard surface cleaners,synthetic and soap-based laundry bars, fabric softeners and fabrictreatment liquids, solids and treatment articles of all kinds willrequire several adjuncts, though certain simply formulated products,such as bleach additives, may require only, for example, an oxygenbleaching agent and a surfactant as described herein. A comprehensivelist of suitable laundry or cleaning adjunct materials can be found inWO 99/05242.

Common cleaning adjuncts include builders, enzymes, polymers notdiscussed above, bleaches, bleach activators, catalytic materials andthe like excluding any materials already defined hereinabove. Othercleaning adjuncts herein can include suds boosters, suds suppressors(antifoams) and the like, diverse active ingredients or specializedmaterials such as dispersant polymers (e.g., from BASF Corp. or Rohm &Haas) other than those described above, color speckles, silvercare,anti-tarnish and/or anti-corrosion agents, dyes, fillers, germicides,alkalinity sources, hydrotropes, anti-oxidants, enzyme stabilizingagents, pro-perfumes, perfumes, solubilizing agents, carriers,processing aids, pigments, and, for liquid formulations, solvents,chelating agents, dye transfer inhibiting agents, dispersants,brighteners, suds suppressors, dyes, structure elasticizing agents,fabric softeners, anti-abrasion agents, hydrotropes, processing aids,and other fabric care agents, surface and skin care agents. Suitableexamples of such other cleaning adjuncts and levels of use are found inU.S. Pat. Nos. 5,576,282, 6,306,812 B1 and 6,326,348 B1.

Method of Use

The present invention includes a method for cleaning a targeted surface.As used herein “targeted surface” may include such surfaces such asfabric, dishes, glasses, and other cooking surfaces, hard surfaces, hairor skin. As used herein “hard surface” includes hard surfaces beingfound in a typical home such as hard wood, tile, ceramic, plastic,leather, metal, glass. Such method includes the steps of contacting thecomposition comprising the modified polyol compound, in neat form ordiluted in wash liquor, with at least a portion of a targeted surfacethen optionally rinsing the targeted surface. Preferably the targetedsurface is subjected to a washing step prior to the aforementionedoptional rinsing step. For purposes of the present invention, washingincludes, but is not limited to, scrubbing, wiping and mechanicalagitation.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are ideally suited for use in homecare (hard surface cleaning compositions) and/or laundry applications.

The composition solution pH is chosen to be the most complimentary to atarget surface to be cleaned spanning broad range of pH, from about 5 toabout 11. For personal care such as skin and hair cleaning pH of suchcomposition preferably has a pH from about 5 to about 8 for laundrycleaning compositions pH of from about 8 to about 10. The compositionsare preferably employed at concentrations of from about 150 ppm to about10,000 ppm in solution. The water temperatures preferably range fromabout 5° C. to about 100° C.

For use in laundry cleaning compositions, the compositions arepreferably employed at concentrations from about 150 ppm to about 10000ppm in solution (or wash liquor). The water temperatures preferablyrange from about 5° C. to about 60° C. The water to fabric ratio ispreferably from about 1:1 to about 20:1.

The method may include the step of contacting a nonwoven substrateimpregnated with an embodiment of the composition of the presentinvention As used herein “nonwoven substrate” can comprise anyconventionally fashioned nonwoven sheet or web having suitable basisweight, caliper (thickness), absorbency and strength characteristics.Examples of suitable commercially available nonwoven substrates includethose marketed under the tradename SONTARA® by DuPont and POLYWEB® byJames River Corp.

As will be appreciated by one skilled in the art, the cleaningcompositions of the present invention are ideally suited for use inliquid dish cleaning compositions. The method for using a liquid dishcomposition of the present invention comprises the steps of contactingsoiled dishes with an effective amount, typically from about 0.5 ml. toabout 20 ml. (per 25 dishes being treated) of the liquid dish cleaningcomposition of the present invention diluted in water.

Composition Formulations Example XXI Granular Laundry Detergent

A B C D E Formula wt % wt % wt % wt % wt % LAS 3-25 5-25 5-25 0-10 0-10C₁₂₋₁₈ Ethoxylate nonionic — — 0-3  — 0-1  surfactant C₁₂₋₁₈ alkylethoxylate sulfate 0-3  0-3  — 0-20 0-3  anionic surfactantPoly-branched cationic 0.01-5    0.01-4    0.01-7    0.01-10   0.01-15  surfactant, amine oxide, soap, alkylpolyglycoside, or betaine accordingto the present invention, and combinations thereof nonionic (AE) andanionic 0-2  0-20 0-5  0-4  0-20 (AS, AES) surfactants derived from theaforementioned polybranched alcohols of the present invention, andcombinations thereof Sodium tripolyphosphate 0-20 0-20 0-20 0-20 0-20Zeolite 0-20 0-20 0-20 0-20 0-20 Silicate builder 0-10 0-10 0-10 0-100-10 Carbonate 0-30 0-30 0-30 5-25 0-20 Diethylene triamine penta 0-1 0-1  0-1  0-1  0-1  acetate Polyacrylate 0-3  0-3  0-3  0-3  0-3 cleaning polymers (modified 0-3  0-3  0-3  0-3  0-3  and unmodifiedpolycarboxylates, ethoxylated amines and derivatives thereof CarboxyMethyl Cellulose  0-0.8  0-0.8 0.2-0.8  0.2-0.8  0.2-0.8  Percarbonate0-10 0-10 0-10 0-10 0-10 Nonanoyloxybenzenesulfonate — — 0-2  0-2  0-2 Tetraacetylethylenediamine — —  0-0.6  0-0.6  0-0.6 Zinc Phthalocyanine— —   0-0.005   0-0.005   0-0.005 Tetrasulfonate Brightener 0.05-0.2 0.05-0.2  0.05-0.2  0.05-0.2  0.05-0.2  MgSO₄ — —  0-0.5  0-0.5  0-0.5Enzymes (lipase, protease,  0-0.5  0-0.5  0-0.5  0-0.5  0-0.5 amylase,and combinations thereof) Minors (perfume, dyes, suds balance balancebalance balance Balance stabilizers) and fillers (eg, sodium sulfate)

Example XXII Liquid Laundry Detergents

A B C D E Ingredient wt % wt % wt % wt % wt % LAS 0 0 5 5 5 alkylethoxylate sulfate 0-10 0-10 0-7 0 0 anionic surfactant alkyl ethoxylatenonionic 14.4%  9.2% 5.4% surfactant Poly-branched cationic 0.01-5   0.01-4   0.01-7   0.01-10   0.01-15 surfactant, amine oxide, soap,alkylpolyglycoside, or betaine according to the present invention, andcombinations thereof nonionic (AE) and/or 0-2  0-20 0-5 0-4   0-20anionic (AS, AES) surfactants derived from the aforementionedpolybranched alcohols of the present invention, and combinations thereofCitric acid 2.0% 3.4% 1.9% 1.0% 1.6% Detergent acid 0-3% 0-8% 0-10%Protease 1.0% 0.7% 1.0% 2.5% Amylase 0.2% 0.2% 0.3% Lipase 0.2% Borax1.5% 2.4% 2.9% Calcium and sodium 0.2% formate Formic acid 1.1% Sodiumpolyacrylate 0.2% Sodium polyacrylate 0.6% copolymer Ethoxylated amine,ethoxylated amine derivative, and combinations thereof DTPA¹ 0.1% 0.9%DTPMP² 0.3% EDTA³ 0.1% Fluorescent whitening 0.15%  0.2% 0.12%  0.12% 0.2% agent Ethanol 2.5% 1.4% 1.5% Propanediol 6.6% 4.9% 4.0% 15.7% Sorbitol 4.0% Ethanolamine 1.5% 0.8% 0.1% 11.0%  Sodium hydroxide 3.0%4.9% 1.9% 1.0% Sodium cumene sulfonate 2.0% Silicone suds suppressor0.01%  Perfume 0.3% 0.7% 0.3% 0.4% 0.6% Opacifier⁴ 0.30%  0.20%  0.50% Water balance balance balance balance Balance 100.0%  100.0%  100.0% 100.0%  100.0%  ¹diethylenetriaminepentaacetic acid, sodium salt²diethylenetriaminepentakismethylenephosphonic acid, sodium salt³ethylenediaminetetraacetic acid, sodium salt ⁴Acusol OP 301

Example XXIII Liquid Dish Handwashing Detergents

Composition A B C₁₂₋₁₃ Natural AE0.6S 270    240    C₁₀₋₁₄ mid-branchedAmine Oxide — 6.0 Poly-branched cationic surfactant, 0.01-5   0.01-4   amine oxide, soap, alkylpolyglycoside, or betaine according to thepresent invention, and combinations thereof nonionic (AE) and anionic(AS, 0-2 0-20 AES) surfactants derived from the aforementionedpolybranched alcohols of the present invention, and combinations thereofC₁₂₋₁₄ Linear Amine Oxide 6.0 — SAFOL ® 23 Amine Oxide 1.0 1.0 C₁₁E₉Nonionic¹ 2.0 2.0 Ethanol 4.5 4.5 Sodium cumene sulfonate 1.6 1.6Polypropylene glycol 2000 0.8 0.8 NaCl 0.8 0.8 1,3 BAC Diamine² 0.5 0.5Suds boosting polymer³ 0.2 0.2 Water Balance Balance ¹Nonionic may beeither C₁₁ Alkyl ethoxylated surfactant containing 9 ethoxy groups.²1,3, BAC is 1,3 bis(methylamine)-cyclohexane. ³(N,N-dimethylamino)ethylmethacrylate homopolymer

Example XXIII Liquid Dish Handwashing Detergents

Composition A B C D E C₁₂₋₁₃ Natural AE0.6S 20   20   Poly-branchedcationic surfactant, 0.01-5 0.01-4    0.01-7 0.01-10   0.01-15 amineoxide, soap, alkylpolyglycoside, or betaine according to the presentinvention, and combinations thereof nonionic (AE) and anionic (AS,   0-20-20   0-5 0-4   0-20 AES) surfactants derived from the aforementionedpolybranched alcohols of the present invention, and combinations thereofC₁₁E₉ Nonionic¹ 2.0 2.0 2.0 2.0 2.0 Ethanol 4.5 4.5 4.5 4.5 4.5 Sodiumcumene sulfonate 1.6 1.6 1.6 1.6 1.6 Polypropylene glycol 2000 0.8 0.80.8 0.8 0.8 NaCl 0.8 0.8 0.8 0.8 0.8 1,3 BAC Diamine² 0.5 0.5 0.5 0.50.5 Suds boosting polymer³ 0.2 0.2 0.2 0.2 0.2 Water Balance BalanceBalance Balance Balance ¹Nonionic may be either C₁₁ Alkyl ethoxylatedsurfactant containing 9 ethoxy groups. ²1,3, BAC is 1,3bis(methylamine)-cyclohexane. ³(N,N-dimethylamino)ethyl methacrylatehomopolymer

Example 11 Automatic Dishwasher Detergent

A B C D E Polymer dispersant²   0.5 5 6 5 5 Carbonate 35  40  40  35-4035-40 Sodium tripolyphosphate 0 6 10   0-10  0-10 Silicate solids 6 6 66 6 Bleach and bleach activators 4 4 4 4 4 Polymer¹ 0.05-10   1   2.5 510  Enzymes 0.3-0.6 0.3-0.6 0.3-0.6 0.3-0.6 0.3-0.6 Disodium citratedihydrate 0 0 0  2-20 0 Poly-branched cationic 0.01-2   0.01-2  0.01-2   0.01-2   0.01-3   surfactant, amine oxide, soap,alkylpolyglycoside, or betaine according to the present invention, andcombinations thereof Water, perfume, dyes and Balance Balance to BalanceBalance Balance other adjuncts to 100% 100% to 100% to 100% to 100% ¹Anamphiphilic alkoxylated polyalkylenimine polymer or any mixture ofpolymers according to any of Examples 1, 2, 3, or 4. ²Such as ACUSOL ®445N available from Rohm & Haas or ALCOSPERSE ® from Alco.

Example 12 Fabric Softener Compositions Weight %'s

Ingredient A B C D Di-polybranched alkyl 10-28 10-28 — — cationicsurfactant accoding to the present invention Di-polybranched diesteralkyl — — 10-28 10-28 cationic surfactant accoding to the presentinvention Hydrochloric acid (25%) 0.12 0.12 0.12  0.12 DC2310 antifoam(10%) 0.15 0.15 0.15  0.15 CaCl2 (25%) 2.1  2.1  2.1  2.1 Soil releasepolymer (40%) 1.25 — — — Ammonium chloride (20%) — — 0.5  0.5 Magnifloc587c (20%) — — — 1.0 Perfume, dye, minors, water balance balance balanceBalance

TEST METHODS

The following two analytical methods for characterizing branching in thepresent invention surfactant compositions are useful:

Separation and Identification of Components in Detergent Alcohols(performed prior to alkoxylation or after hydrolysis of alcohol e foranalytical purposes). The position and length of branching found in theprecursor detergent alcohol materials is determined by GC/MS techniques[see: D. J. Harvey, Biomed, Environ. Mass Spectrom (1989). 18(9),719-23; D. J. Harvey, J. M. Tiffany, J. Chromatogr. (1984), 301(1),173-87; K. A. Karlsson, B. E. Samuelsson, G. O. Steen, Chem. Phys.Lipids (1973), 11(1), 17-38].

Unless otherwise noted, all component or composition levels are inreference to the active level of that component or composition, and areexclusive of impurities, for example, residual solvents or by-products,which may be present in commercially available sources.

All percentages and ratios are calculated by weight unless otherwiseindicated. All percentages and ratios are calculated based on the totalcomposition unless otherwise indicated.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

All documents cited in the Detailed Description of the Invention are,are, in relevant part, incorporated herein by reference; the citation ofany document is not to be construed as an admission that it is prior artwith respect to the present invention.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention

1. A surfactant composition comprising one or more surfactantderivatives of isomers of acyclic detergent alcohol having 11, 16, or 21carbon atoms and two, three, four or five methyl or ethyl branches ormixtures thereof wherein the surfactant derivatives are selected fromthe group consisting of cationic surfactants, zwitterionic surfactants,amine oxide surfactants, alkylpolyglycoside surfactants, soaps, fattyacids, di-long-chain alkyl cationic surfactants and mixtures thereof. 2.A surfactant composition according to claim 1 wherein greater than 70%of the acyclic surfactant derivatives comprise two, three or four methylgroups.
 3. A cleaning composition comprising the surfactant compositionaccording to claim
 1. 4. A cleaning composition comprising thesurfactant composition according to claim
 2. 5. A fabric softeningcomposition comprising the surfactant composition according to claim 1